Antimony Pentafluoride/Graphite Catalyzed Oxidative Carbonylation of Methyl Halides with Carbon Monoxide and Copper Oxides (or Copper/Oxygen) to Methyl Acetate

Article abstract of DOI:10.1021/jo00301a017

Superacidic antimony pentafluoride/graphite catalyzed oxidative carbonylation of methyl halides with carbon monoxide and copper oxides (or copper metal and oxygen) gives methyl acetate (AcOMe).The reaction was investigated in a pressure reactor in the temperature range of 100 to 300 deg C and pressures of 20 to 150 atm.The oxidative carbonylation of methyl bromide (MeBr) with CO and Cu2O at 270 deg C under a pressure of 130 atm gave 48 mol percent Me2O and 33 mol percent AcOMe.Replacing Cu2O with CuO gave about 40-50percent AcOMe, with 10-20percent Me2O.Using Cu and O2 gave ca. 50percent AcOMe, with 5percent Me2O.In the reaction 5-10percent MeF is also formed due to halogen exchange.The reactivity of the methyl halides shows the decreasing order of MeBr > MeCl > MeF.